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| United States Patent |
6,103,801
|
|
Gracey
, et al.
|
August 15, 2000
|
2-substituted succinate esters
Abstract
This invention relates to a process for producing 2-substituted succinate
esters of formula (I) by reacting (a) a dicarboxylic compound with a first
alcohol R'O[CH'.CH.sub.2 O].sub.x H where x is 0 or an integer from 1-6 in
the presence of a catalyst to form a hydrocarbyl ester or, when x=1-6, a
hydrocarbyloxy alkylene ester of maleic and/or fumaric acid and (b) the
ester from step (a) with an alkaline earth metal alkoxide in the presence
of a second alcohol R.OH to form the 2-substituted succinate ester of
formula (I). The esters and paint formulations based thereon are also
claimed.
| Inventors:
|
Gracey; Benjamin Patrick (Hull, GB);
Hallett; Christopher (Watford, GB)
|
| Assignee:
|
BP Chemicals Limited (London, GB)
|
| Appl. No.:
|
019353 |
| Filed:
|
February 5, 1998 |
Foreign Application Priority Data
| Jun 28, 1996[GB] | 9613679 |
| Nov 27, 1996[GB] | 9624680 |
| Current U.S. Class: |
524/308; 560/181; 560/182; 560/183; 560/198; 560/201; 568/828; 568/909.5 |
| Intern'l Class: |
C08K 005/12; C07C 067/08; C07C 069/708 |
| Field of Search: |
560/181,182,183,198,201
524/308
568/909.5,828
|
References Cited
U.S. Patent Documents
| 2221663 | Nov., 1940 | Rothrock | 560/198.
|
| 2346612 | Nov., 1944 | Rothrock | 560/198.
|
| 2404313 | Jul., 1946 | Rodman.
| |
| 2571212 | Oct., 1951 | Croxall et al. | 260/484.
|
| 3172904 | Mar., 1965 | Rehfuss.
| |
| 3303241 | Feb., 1967 | Moorshead | 260/884.
|
| 3499042 | Mar., 1970 | Smutny | 260/614.
|
| 5118885 | Jun., 1992 | Tokitoh et al. | 568/909.
|
| Foreign Patent Documents |
| 552715 | Apr., 1943 | GB.
| |
| WO 97/02230 | Jan., 1997 | WO.
| |
| WO 97/02229 | Jan., 1997 | WO.
| |
Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Fay, Sharpe, Fagan, Minnich & McKee, LLP
Parent Case Text
This application is a continuation of co-pending International Application
No. PCT/GB97/01742 filed on Jun. 27, 1997.
Claims
What is claimed is:
1. A process for producing 2-substituted succinate esters of the formula
(1) and process comprising reacting
a. a dicarboxylic compound selected from the group consisting of maleic
acid, maleic anhydride, fumaric acid and the dialkyl ester of maleic or
fumaric acid with an alcohol R.sup.1 O[CHR.sup.11 CH.sub.2 O].sub.x H
where x is 0 or an integer from 1-6 in the presence of an esterification
catalyst to form a hydrocarbyl ester or, when x=1-6, a hydrocarbyloxy
alkylene ester of maleic and/or fumaric acid and
b. the hydrocarbyl or hydrocarbyloxy alkylene ester from step (a) with an
alkaline earth metal alkoxide in the presence of a further amount of the
alcohol to form the 2-substituted succinate ester of formula (I)
##STR6##
in which R.sup.1 =R and is an unsaturated hydrocarbyl or allyically
unsaturated is hydrocarbyloxy allylene group having at least 5 carbon
atoms,
R.sup.11 is H or an alkyl or an alkylene group having 1 to 2 carbon atoms
and,
each of a and b is same or different and has a value of 0 or is an integer
from 1-6.
2. A process according to claim 1 wherein R.sup.1 is derived from the
reactant alcohol R.sup.1 O[CHR.sup.11 CH.sub.2 O].sub.x H where x is 0 or
an integer from 1-6 which is used for making the succinate ester.
3. A process according to claim 1 wherein the reactant alcohol is an
allylic alcohol selected from the group consisting of 2-ethyl-hex-2-en-1
-ol; 2-octen-1 -ol; 1-octen-3-ol; 2,7-octadienol; 2-ethyl allyl alcohol;
hept-3-en-2ol; 4-methyl pent-3-en-2-ol; 4-t-butoxy but-2-en-1 -ol;
4-n-butoxy but-2-en-1-ol; cinnamyl alcohol; and isophorol.
4. A process according to claim 1 wherein the esterification catalyst used
is selected from zinc acetate, dibutyl tin oxide, stannous oxalate,
para-toluene sulphonic acid and phosphoric acid.
5. A process according to claim 1 wherein the reaction for making succinate
esters of formula (I) is carried out at a temperature below 120.degree. C.
6. A process according to claim 1 wherein the ester product from this step
(a) is then further reacted in a step (b) with a further amount of the
reactant alcohol in the presence of an alkaline earth metal alkoxide
catalyst at a temperature below 120.degree. C. and at a pressure in the
range from atmospheric to 50 Kpa to enhance the amount of the desired
2-succinate ester in the product from step (a) at the expense of the
maleates and fumarates in said product.
7. A process according to claim 6 wherein the alkaline earth metal alkoxide
is magnesium alkoxide.
8. A process according to claim 7 wherein reaction of 2-ethyl hexenol with
maleic acid or anhydride followed by reaction of the product with
magnesium alkoxide of 2-ethylhexenol as catalyst gives rise to a product
which primarily comprises 2- (2-ethyl hexenoxy) -di [2- (2-ethyl hexenyl)]
succinate.
9. A process according to claim 3 wherein reaction of octadienoxy ethanol
with maleic acid or anhydride followed by the reaction of the product with
the magnesium alkoxide of octadienoxy ethanol as catalyst gives rise to a
product comprising di-2-(octadienoxy)ethyl)-2-(2-octadienoxy)ethoxy)
succinate.
10. A paint or coating formulation based on alkyd resins and comprising
2-octadienoxy di-octadienyl succinate as a reactive diluent in a paint or
coating.
11. A paint or coating formulation based on alkyd resins according to claim
10 wherein said formulation also contains one or more of butylated
hydroxy-toluene (2,6-butoxy-4-methyl phenol) and 2,4,6-tert-butyl phenol
to inhibit haze and/or peroxidation.
12. 2-octadienoxy di-octadienyl succinate.
Description
This invention relates to a process for producing 2-substituted succinate
esters with low colour and use of said ether esters as diluents in paint
and polymer formulations,
One of the processes used hitherto to produce 2-substituted succinate
esters is the combined transesterification and Michael addition reaction
of an alcohol or a monoether of a polyoxyalkylene glycol as described in
GB-A-552715 in which ether esters of hydroxysuccinic acid and unsaturated
alcohols are prepared by reacting in a single step under anhydrous
conditions an alkyl ester of maleic acid with an unsaturated alcohol in
the presence of a magnesium alkoxide catalyst. However, this method when
repeated for instance with an octadienol/di methyl maleate system using
magnesium methoxide as a catalyst gives products which have a deep red
colour. It may be possible to overcome this colour problem in the products
described in this prior art by distillation. However, such a method is
unlikely to be practicable with the synthesis of esters contemplated in
the present invention since they are all meant to have relatively low
volatility and hence are not amenable to purification by distillation.
It has now been found that 2-substituted succinate esters some of which are
novel, can be produced in commercially viable yields and purity by using a
two-stage process.
Accordingly, the present invention relates to a process for producing
2-substituted succinate esters of the formula (1) said process comprising
reacting
a. a dicarboxylic compound selected from the group consisting of maleic
acid, maleic anhydride, fumaric acid and the dialkyl ester of maleic or
fumaric acid with an alcohol R'O[CH.sub.2 O], H where x is 0 or an integer
from 1-6 in the presence of a catalyst to form a hydrocarbyl ester or,
when x=1-6, a hydrocarbyloxy alkylene ester of maleic and/or fumaric acid
and
b. the ester front step (a) with an alkaline earth metal alkoxide in the
presence of a further amount of the alcohol to form the 2-substituted
succinate ester of formula (1)
##STR1##
in which R and R' are each an unsaturated hydrocarbyl or allyically
unsaturated hydrocarbyloxy alkylene group having, at least 5 carbon atoms,
R" is H or an alkyl or an alkylene group having 1 to 2 carbon atoms and,
each of a and b is same or different and has a value of 0 or is an integer
from 1-6.
By the expression "alkylene" as used herein and throughout the
specification is meant a divalent hydrocarbyl group such as eg a
--CH.sub.2 (CHR")--CH.sub.2 -group wherein, **=0 or an integer and R" has
the same notation as above.
R' is derived from the reactant alcohol R'O[CHR".CH.sub.2 O].sub.x H where
x is 0 or an integer from 1-6 which is used for making the succinate ester
and can be an allylic hydrocarbyl or an allylic hydrocarbyloxy alkylene
group. Thus, the reactant alcohol is an allylic alcohol and includes inter
alia 2-ethyl-hex-2-en-1-ol;- 2-octen-1-1-octen--3-ol; 2,7-octadienol,
2-ethyl allyl alcohol; hept-3-en-2-ol; 4-methyl pent-3-en-2-ol; 4-t-butoxy
but-2-en-1-ol (also called 1,4-but-2-ene diol mono-tertiary butyl ether);
4-n-butoxy but-2-en-1-ol (also called 1,4-but-2-ene diol mono-n-butyl
ether): cinnamyl alcohol; and isophorol.
The reactant alcohol, R'O[CHR".CH.sub.2 O].sub.x H where x is 0 or an
integer from 1-6 can be prepared in several ways known to those skilled in
the art. For instance, this reactant alcohol, eg an allylic alcohol, can
be produced by the reduction of the corresponding .alpha.,
.beta.-unsaturated aldehyde eg by hydrogenation, which will generate a
mixture of the allylic alcohol and its saturated analogue. Some other
allylic alcohols may be produced from conjugated dienes via the well known
addition reactions. Furthermore, other allylic alcohols may be produced by
by hydrolysis of the ester to a mixture of isomeric allylic alcohols. This
litter reaction may, like some of the other reactions mentioned above,
result in & mixture of products which includes inter alia the desired
allylic alcohol, isomers thereof and saturated analogues thereof. The
mixtures of allylic alcohol with the saturated analogue thereof and/or the
isomers thereof can be then used as such or, after further purification to
isolate the desired allylic alcohol, to prepare the esters represented by
formula (I) above.
Where the reactant alcohol is itself an allylic unsaturated hydroxy ether.
ie x 1.6, this may be derived by alkoxylation of an alcohol. eg allylic
ether alcohol, suitably in the presence of a catalyst to form the hydroxy
ether. Where a catalyst is used it should be such that it does not cause
rearrangement of the allylic function and hence, amphoteric, basic or
acidic catalysts may be used. The catalyst can be heterogeneous or
homogeneous. The alkoxylation step is suitably carried out in the presence
of a base catalyst. Examples of base catalysts that may be used include
alkali metal hydroxides such as sodium or potassium hydroxide and other
metal salts such as potassium acetate.
The alkoxylation reaction to form the hydroxy ether of the allylic alcohol
can be carried out using one or more of the epoxides which include inter
alia ethylene oxide propylene oxide, butene oxide and butadiene
mono-oxide. The amount of epoxide used for this step) would depend upon
the number of alkoxy groups desired in the hydroxy ether. The amount of
epoxide used is suitably in the range from 0.1 to 20 moles, preferably
from 1 to 5 moles based on the allylic alcohol reactant.
The alkoxylation reaction is suitably carried out at a temperature in the
range from 50 to 180.degree. C., preferably from 60 to 140.degree. C. The
reaction pressure for this step is suitably autogenous but is preferably
front 100 to 700 KPa.
The hydroxy ether formed in this step) is suitably separated from the
reaction mixture by neturalisation using, eg magnesium silicate, then
filtered to remove the neutralising agent and the salt of neutralisation
so formed to leave behind filtrate comprising the desired hydroxy ether.
The hydroxy ether so produced can be used either as such without
purification, or, optionally, after purification (eg by distillation) for
the esterification stage.
Thus, the 2-succinate esters of formula (1) are prepared by reacting in the
first stage (a) the reactant alcohol wall maleic acid or anhydride and/or
fumaric acid or esters thereof in the presence of a catalyst. The catalyst
used in this step can be zinc acetate, dibutyl tin oxide, stannous
oxalate, para-toluene sulphonic acid or phosphoric acid. This reaction is
suitably carried out at a temperature below 150.degree. C. preferably from
100-130.degree. C. The completion of the reaction is ascertained by GC
analysis using a CP-SILS 50 m capillary column and a flame ionisation
detector. Upon completion of the reaction the unreacted materials are
stripped out by steam stripping or by azeotropic distillation eg using an
azeotroping agent such as eg cyclohexane. The catalyst may then be
neutralised or removed as appropriate, the solids filtered and the ester
in the filtrate recovered.
The ester product from this step (a) is then further reacted in a step (b)
with a further amount of the reactant alcohol in the presence of an
alkaline earth metal alkoxide catalyst. The function of this step (b) is
to enhance the amount of the desired 2-succinate ester in the product from
step (a) at the expense of the maleates and fumarates in said product. The
alkaline earth metal alkoxide may be derived from the .second reactant
alcohol or from another alcohol. The alkaline earth metal alkoxide is
preferably magnesium alkoxide. The amount of alkaline earth metal alkoxide
used must be sufficient to compensate for loss of catalyst due to its
reaction with any residual acids or water present in the products from
stage (a) of the reaction or the reactant alcohol, The reaction with the
alkaline earth metal alkoxide is suitably carried out at a temperature
below 120.degree. C. suitably in the range from 40 to 50.degree. C. and
step (b) is suitably carried out at atmospheric, subatmospheric or
superatmosphesic p1pressures. The pressures used are preferably in the
range from atmospheric to 50 Kpa, more preferably from atmospheric to 5
KPa. This division of the reaction into two stages allows the use of
relatively milder condition than has hitherto been possible and as a
consequence affords an improved product which is less coloured.
The esters formed by this process may be a mixture of the desired esters of
formula (1) and the corresponding unsaturated analogues comprising the
maleic acid or fumaric acid esters. Thus, for example, reaction of 2-ethyl
hexenol with maleic acid or anhydride followed by reaction of the product
with magnesium alkoxide of2-ethylhexenol as catalyst would give rise to a
product which primarily comprises 2-(2-ethyl hexenoyl)-di[2-(2-ethyl
hexenyl)) succinate. Similarly, when octadienoxy ethanol is reacted with
maleic acid or anhydride, followed by the reaction of this product with
the magnesium alkoxide of octadienoxy ethanol as octadienoxy) ethoxy]
succinate. Both of these are novel esters not reported hitherto.
Similarly, when 2,7-octadienol is reacted with dimethyl maleate, followed
by reaction or the resultant product with further aliquots of the reactant
alcohol in the presence of magnesium alkoxide catalyst, the product
obtained is 2-octadienoxy di-octadienyl succinate.
A feature of the two-stage process of the present invention is that it uses
relatively milder conditions than a conventional Michael addition
reaction, For instance, no reflux conditions need be used during this
step. Furthermore, the present process enables the proportion of the
2-substituted succinate ester in the reaction product to be enhanced
considerably without leading to undesirable polymer formation or
increasing the colouration of the ester product. Moreover, the present
process gives better yields of the desired 2-substituted succinate ester
due to the milder conditions employed.
The esters of the present invention have low volatility and relatively low
viscosity suitably below 1500 mPa.s, thereby rendering them a suitable
solvent component for curable paint and varnish formulations. These ether
esters are especially suitable as the so called "reactive diluents" for
paint formulations and in particular those containing alkyl resins.
Reactive diluents are usually compounds or fixtures of compounds of
relatively low viscosity, a relatively high boiling point (or low
saturated vapour pressure) which act as solvents during the formulation
and processing of the coating. An advantage of reactive diluents is that
such diluents fail copolymerise with components of the alkyl resin. Hence
reactive diluents may be used Lo replace part or all of the traditional
solvents normally used in such formulations thereby reducing losses of the
solvent to atmosphere on drying of the coating. Use of reactive diluents
comprising esters of polyhydric alcohols which have been partially
etherified with ally alcohol are described in EP-A-0 253 474.
Alkyd resins are well known components of decorative paints (see, for
example, "The Technology of Paints, Varnishes and Lacquers" by C R
Martens(Ed.). published by Robert Krieger Publishing (1974) and can be
prepared from polybasic acids or anhydrides, polyhydric alcohols and fatty
acids or oils. U.S. Pat. No. 3,819,720 describes methods of preparing such
alkyd formulations. Alkyd coating compositions usually contain large
amounts of solvents (eg of solvents (eg mineral spirits and aromatic
hydrocarbons).
The compositions of the present invention are highly suitable for use as
reactive diluents. The relative ratios of reactive diluent to the alkyd
resin in a formulation can be derived from the ranges quoted in published
EP-A-0 305 006. In an example in which the reactive diluent replaces all
of the traditional solvent, the ratio of reactive diluent to alkyd resin
is suitably in the range from 1-50: 99-50 parts by weight, eg 5-50: 95-50,
preferably from 5-25: 95-75 and more preferably from 5-15 95-85 parts by
weight. On the other hand, where used in a conventional paint formulation,
such a diluent can replace all or part of a traditional solvent such as
white spirit. The formulations may contain further components such as
catalyst, drier, antiskinning agent, pigments, pigment stablisers,
rheology controllers (eg. for sag control). UV and oxidation stabilisers,
flow additives, microgels (e.g. to enhance hardness) and other additives.
The formulations may also need to include water scavengers such as
trialkyl orthoformates, molecular sieves or zeolites where the reactive
diluent used is susceptible to hydrolysis such as eg some of the ether
ester derivatives. Furthermore, where such water scavengers are used it
may be necessary to use them in combination with compatible pigment
stabilizers. Where a drier (siccative) is used this may further contribute
towards the solvent content of the formulation.
For formulations comprising an oxidatively curing alkyd resin and a
siccative/drier such as cobalt complexes, impurities which can have a
co-ordination affinity for the siccative drier such as cobalt complexes
can affect adversely the drying speed and stability of the paint. Examples
of such impurities include maleic acid and triethyl amine. In particular
it has been found desirable to minimise the acidity of the ester mixture
used as reactive diluent in such formulations to a value of <7000 ppm,
preferably 3000 ppm, more preferably <1000 ppm w/w of KOH.
It has also been found that when a mixture of esters, ie the succinates
fumarates and maleates, is used as a reactive diluent in such formulations
comprising an oxidatively curing alkyd resins, the properties/performance
of the diluent call be varied by changing the relative proportions or the
three esters present ill Such a diluent. For example, mixtures with a
relatively lower amount of maleates exhibit better hardness and drying
properties compared with those having relatively higher amounts of such
maleates. Moreover, it has also been observed that formulations comprising
these esters display a decreased tendency towards wrinkling. This renders
them particularly suitable when using formulations comprising high solid
systems/one-coat paints have to be applied to generate a greater thickness
of the relevant coating without impairing the ability of such thicker
layers to harden through.
For some uses it is preferable that the free alcohol content of the diluent
is minimised in order to facilitate drying of the formulations A feature
of the: present invention is that other esters of formula (l) when used as
reactive diluents in paint or coating formulations, especially those
comprising alkyd resins, enhance the performance of these formulations- In
particular, where a mixture of products comprising ether esters of the
present invention derived by reacting an allylic alcohol or a hydroxy
ether thereof with maleic, acid/anhydride or fumaric acid is used as
reactive diluent, they enhance their performance when compared with that
of the unsaturated esters when used alone.
A further aspect of the present invention is that such esters when used in
a relatively pure state do not cause any haze in the formulation, Where
there is likely to be a risk of such haze formation, eg due to the
presence of impurities such as eg resins or polymers formed during the
synthesis of the esters used or during storage is of such formulations, it
is beneficial to use inhibitors such as eg butylated hydroxy-toluene
(2,6-butoxy-4-methyl phenol) or 2,4.6-tert-butyl phenol. Such inhibitors
not only have the advantage of preventing haze formation but also render
the formulations safer to handle by inhibition of other unwanted reactions
in the formulation such as eg peroxidation.
Uses of the molecules of this invention include the partial or total
replacement of traditional hydrocarbon-based solvents in solvent-borne
alkyd paints used for primer undercoat and topcoat decorative applications
as well as in industrial applications such as alkyd primers and UV-cure.
The molecules of this invention are also suitable for use as co-monomers,
for example in vinyl acetate-based polymers used in emulsion paints. In
this case, the molecules of this invention impart a temporary
plasticisation to the paint film, before air-curing to a hard finish. They
can, therefore, facilitate the partial or total replacement of coalescent
solvents,
In addition, the molecules could be used in water-based paints based on
acrylic and alkyd resins, in addition to, or instead of, coalescent
solvents,
The present invention is further illustrated with reference to the
following Examples.
EXAMPLE 1: General Method: Reaction of an allylic ether-alcohol with a
maleate
The following apparatus was assembled:
A five-liter flanged flask with an insert pipe for a nitrogen sparge, a
thermowell for thermocouple, and a Dean and Stork apparatus with
double-walled condenser. The flask was heated with an electric heating
mantle which was controlled with a eurotherm controller connected to the
thermocouple. The nitrogen sparge pipe was inserted so that the nitrogen
flow agitated the flask contents and provided mixing during the course of
the reaction. The nitrogen flow also served to entrain out the liberated
methanol and force the reaction to completion.
To the flask was added dimethyl maleate (914.3 g). 2,7-octadienol (2375 g)
and stannous oxalate (31.2 g). The mixture was sparged with nitrogen for
10 minutes to remove air and the nitrogen flow was then reduced to a level
which ensured efficient mixing. The mixture was then heated in stages to
130.degree. C. (e.g. 80.degree. C. for 10 minutes, then 100.degree. C. for
10 minutes and then 180.degree. C. for 10 minutes). The progress of the
reaction was monitored by collection of the methanol collected in the Dean
and Stark apparatus. In order to drive the reaction to completion the
temperature was raised to 140.degree. C. after 7 hrs at 130.degree. C.
When 90% of the methanol had been collected, the reaction mixture was
sampled hourly and analysed by GC.
The reaction was adjudged complete when the level of the "half ester"
(methyl octadienyl maleate/fumarate) fell to below 0.3% w/w and this took
approximately 31 hours. At this point the heating was switched off and the
reaction mixture allowed to cool to room temperature. The product from the
reaction was then decanted from any solids in the reaction flask. This
product was then charged to a heated, decanter (40.degree. C.) with an
equal volume of 5% w/w aqueous sodium hydroxide solution. The mixture was
stirred for 20 minutes and then allowed to separate and the lower aqueous
phase decanted. This base wash was repeated and the remaining organic
phase was washed with saturated brine until the aqueous phase reached a
steady pH. The organic phase was then heated (100.degree. C.) under
reduced pressure (<500 Pa (<5 mBar)) on a rotatory evaporator to remove
residual water and the majority of the excess octadienol. After cooling,
the product was filtered and transferred to a 5-liter three-necked
round-bottomed quickfit flask t-his flask was equipped with a still-head
condenser and receiver flask (Perkin triangle), a thermocouple, a stream
inlet pipe, and a eurotherm controlled heating mantle. The apparatus was
evacuated to 4000 Pa (40 mBar) and the product heated to 120.degree. C.
The supply of steam was then connected and the residual traces of
octadienol were removed. The purification was judged complete when the
volume of the heads product aqueous phase to increased more than times
that of the organic phase. Alter cooling down the product was then treated
with activated carbon (1% w/w, 100.degree. C. 2 Hrs, <500 Pa (<5 mBar)) on
a rotatory evaporator. The cooled mixture was filtered through dried
celite to obtain the final product which had the following analyses:
______________________________________
OH number 4 mg KOH/g (titration)
total acid 46 ppm KOH/g (titration)
maleic acid/anhydride <10 ppm (HPLC)
Fumaric acid <10 ppm (HPLC)
tin <10 ppm (atomic absorption)
sodium <20 ppm (atomic absorption, detection limit)
chlorine <10 ppm (atomic absorption, detection limit)
GC "CPSil5" column octadienyl methyl fumarate/maleate (0.11% w/w)
di-(2,7-octadienyl) maleate (73% w/w)
di-(2,7-octadienyl) fumarate (22% w/w)
2-(2,7-octadienoxy) di-(2,7-octadienyl) succinate
(3% w/w)
______________________________________
The GC assignment was supported by GC/MS and a .sup.1 H nmr and .sup.13 C
nmr studies, The GC/MS used a VG Trio-1000, operated according to the
manufacturers instructions under the following conditions:
GC column 25 m.times.0.32 mm DB5 (0.25 micron film)
temperature programme 40.degree. C. (3 mins)@10C/min 320.degree. C.(10
mins)
injection 1 microliter (1% solution in acetone) on column 40.degree. C.
ammonia chemical ionisation (CI)
scan range 50-800
scan rate l/s
It was found that the deductions of molecular weights from the Cl spectra
is rather less straightforward than is usual on account of (a) extensive
rearrangements of fumarates in particular giving [M+3] and [M+20] ions in
addition to the usual [M+1] and [M+18] ions and (b) extensive
fragmentation exhibited by some species. As a result the GC peaks were
assigned by interpretation. In addition to the assigned peaks an
additional species was identified which was assigned to a lactone. These
assignments were confirmed by .sup.1 H and .sup.13 C nmr. Table 1 gives
tentative assignments of the observed .sup.13 C nmr peaks. It should be
noted that the two isomeric octadienols (2,7-octadienol and
1.7-octadien-3-ol) though not separable by the GC method used can be
identified by nmr and are recorded in the nmr assignment Table 1. The
correspondence to the GC was confirmed again by integration of the nmr
spectrum of several samples in which the composition varied. The lactone
found by GC/MS was also observed in the nmr and quantified at
approximately 6.:2% (tentative structure given in Table 1).
TABLE 2
__________________________________________________________________________
2,7-Octadienol;
#STR2##
-
1 2 3 4 5 6 7 8
__________________________________________________________________________
Major 63 132.8 129.5 31.3 28.6 33 138.5 114.5
Minor 58 132 129 26.6 28 33 135.5 114.5
__________________________________________________________________________
-
Fumarate/Maleate
#STR3##
-
Fumarate/Maleate
1 2 3 4 5 6 7 8 9 10
__________________________________________________________________________
Maleate 65.24 123.34 135.81 31.12 27.53 32.65 137.8 114.3 164.27 129.33
(major isomer)
Maleate 60.4 -- -- 26.39 28.04 32.65 -- -- 164.42 129.39
(minor isomer)*
Fumarate 65.35 123.31 136.16 31.2 27.58 32.73 137.81 114.42 163.96
133.12
(major isomer)
Fumarate 68.72 122.83 135.02 26.49 28.1 32.79 137.81 114.51 164.07
133.21
(minor isomer)*
-
2-(2,7-octadienoxy)di-2,7-octadienyl succinate:
#STR4##
- NB Due to the loss of symmetry (of maleate of fumarate) in the
molecule, all the octadienyl/octadienoxy
groups are magnetically inequivalent.
1 2 3 4,4',4"
5,5'
6,6',6"
7,7'
8,8'
9 10 11 12
__________________________________________________________________________
Major 65.15 123.52 135.9 31.2 27.58 32.73 137.81 114.51 169.18 37.53
73.51 170.69
Minor 60.31 -- -- 26.49 28.1 32.79 -- -- 169.27 -- 73.7 170.78
__________________________________________________________________________
1' 2' 3' 1" 2" 3" 5" 7" 8"
__________________________________________________________________________
Major 64.94 123.75 135.38 71.24 125.66 134.55 27.76 137.96 114.2
Minor 60.13 -- -- 65.89 --
-- -- -- --
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Lactones: Species believed to be lactones have been identified in the
octadienyl ester samples. Whilst there appear to
be two possible isomers of this lactone, the .sup.13 C NMR data fits
the structure:
-
#STR5##
-
11' 2 3 9 10 11 12 1'
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Isomer 1 71.28 41.47 125.33 170.49 30.45 39.47 176.43 64.94
Isomer 2 69.81 45.00 126.58 170.01 31.69 41.59 176.30 64.94
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The mixed ester product from step (a) comprising a relatively low amount
the 2-succinate ester is reacted in a step (b) with a second reactant
alcohol in the presence of a magnesium alkoxide catalyst as follows:
Step (b): Allyloxysuccinate Enhancement--General method All apparatus used
was dried (10.degree. C. oven) before use and the liquid agents were be
dried ( <0.05% w/w water--molecular sieves 3a). The total acid number
(TAN) of the ester reagent was measured.
To a conical flask was charged a pear shaped magnetic follower:
______________________________________
The mixed ester product from step (a)
546.6 g
2,7-Octadienol 414.82 g
magnesium ethoxide # 4.858 g
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#[assuming that 1 mole of acid is neutralised by 1 mole of magnesium
ethoxide,
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1 ppm KOH/g is =
1 .times. 10.sup.-6 /Mol Wt of KOH
moles KOH/g
1 .times. 10.sup.-6 /56.11 moles KOH/g
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The molecular weight of magnesium ethoxide =114.44
So TAN of 1 ppm KOH will require 114.44.times.1.times.10.sup.-6 /56.11 g
If the sample weighs Y grams, if the sample TAN is Z ppm/KOH then the
amount of magnesium ethoxide required to neutralise the acid in the
sample=114.44.times.Y.times.Z.times.1.times.10.sup.-6 /56.11.
To this amount must be added the amount of magnesium ethoxide needed to
catalyse the reaction eg 035% w/w.]
A nitrogen top cover was supplied to the flask and the mixture with
magnetic stirring heated to 80.degree. C. The reaction was monitored by GC
and samples withdrawn at different degrees of conversion.
The samples were purified by using the following procedure.
An equal volume of saturated brine was added to the sample in the
separating funnel and the mixture shaken for 5 minutes. The mixture
separated into two phases, an upper organic phase and a lower aqueous
phase. The lower aqueous phase was decanted and the procedure repeated
until the the aqueous layer pH deceased to 7.+-.0.5. To the upper organic
phase was added 1% w/w activated carbon and the mixture was heated to
100.degree. C. for the at 133.3 Pa (1 mmHg) on a rotatory evaporator. The
material was then allowed to cool to room temperature and filtered through
a cake of dried celite filter aid. It was found that was possible to
obtain conversions of the maleate starting material to the
allyloxysuccinate ill excess of 97% by this method.
2. Testing of reactive diluents in paint formulations:
A good reactive diluent must meet a range of criteria including low odour
and toxicity, low viscosity and the ability to "cut" the viscosity of the
paint to facilitate application on the surface to be coated therewith.
Furthermore, the diluent should not have a markedly adverse effect on the
properties of the paint film such as drying speed, hardness, degree of
wrinkling, durability and tendency to yellowing. The reactive diluents
described above have therefore been tested in paint applications using
both clear and pigmented paints. The diluents have been compared with
paints formulated using white spirit, a conventional thinner.
2.1 Unpigmented "Clearcoat" Formulations:
2.1.1 Materials Used
Unpigmented ("clearcoat") paint formulations were prepared using a high
solids alkyd resin SETAL.RTM.EPL 91/1/14 (ex AKZO NOBEL, and described in
"Polymers Paint and Colour Journal, 1992, 182, pp. 372). In addition to
the diluent. Siccatol.RTM.938 drier (ex AKZO NOBEL) and methyl ethyl
ketone-oxime (hereafter "MEK-oxime") anti-skinning agent were used. Where
used, the white spirit was Exxon type 100. The nominal proportions of the
above materials in the paint formulators were:
TABLE 2
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Materials Parts by weight
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Resin + Diluent
100.0
Siccatol 938 6.7
MEK-oxime 0.5
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Note that, for white spirit formulations only, the proportions of drier
and antiskinning agent were calculated on the basis of the resin only.
Thus, the concentration of these components in the paint was lower than
for other diluents.
2.1.2 Method of Preparation of Clearcoat Formulations:
Alkyd resin and diluent (2-(2.7-octadienoxy)-di-2,7-octadienyl succinate)
were mixed in glass jars for 2 hours (eg using a Luckhain multi-mix roller
bed) in the proportions required to achieve a viscosity (measured via the
ICI cone and plate method using a viscometer supplied by Research
Equipment (London) Limited) of 68.+-.3 Pa.times.(6.8.+-.0.3 poise).
Typically, this resulted it, a mixture which was ca. 85% w/w resin. If
further additions of diluent or resin were required to adjust the
viscosity to 68.+-.3 Pa s (6.8 .+-.0.3 poise). a further hour of mixing
was allowed. The required quantity of drier was added and, after mixing (1
hour). the required amount of anti-skinning agent was added, after final
mixing for at least 30 minutes, the viscosity of the mixture was measured
to ensure that the viscosity was between 61 and 69 Pa s (6.1 and 6.9
poise).
The mixture ("formulation") was then divided into two jars so as to leave
ca. 10-15% v/v headspace of air in the sealed jars. One of the jars was
stored at 23.degree. C. in darkness for 7 days before paint applications
tests were performed. The second jar was stored ("aged") at 35.degree. C.
in daylight for 14 days before applications tests were performed.
3. Test Procedures used for Clearcoat Formulations:
3.1 Application of paint films:
Thin films were applied to cleaned glass test plates using Sheen cube or
draw-bar applicators with a nominal 75 .mu.m gap widths
3.2 Viscosity measurements and results:
The viscosity of each diluent was measured at 23.degree. C. using a
suspended level viscometer. Densities of the diluents were taken as an
average of three readings made at 25.degree. C. using density bottles with
a nominal 10 cm.sup.3 capacity, calibrated with water.
TABLE 3
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Viscosity of reactive diluents
Diluent Viscosity (m Pa.s)
______________________________________
AK2R (Example S3)
18
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3.3 Drying Performance:
Drying performance was measured using films applied to 30 cm.times.2.5 cm
glass strips and BK drying recorders. The BK recorders were enclosed in a
Fisons controlled temperature and humidity cabinet so that the drying
experiment could be performed at 10.degree. C. and at 70% relative
humidity. Sample performance was assessed on the basis of the second stage
of drying (dust drying time, T2)
TABLE 4
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SAMPLES PREPARED BY THE ABOVE PROCESS USING
MAGNESIUM ETHOXIDE & TEST DATA
Fresh Aged
Drying Drying
Times Times
Solvent Description (hrs) (hrs)
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Solvent-1
Di-octadienyl maleate prepared with 0.1%
11.88 13.86
MSA and treated with magnesium 9.26 13.09
ethoxide (7% succinate, reaction
interrupted)
Solvent-1 treated further with magnesium 7.6 9.53
ethoxide (58% succinate)
Solvent-2 Dioctadienyl maleate prepared with 0.1% 10.47 13.56
dibutyl tin oxide
Solvent-2 treated with magnesium 6.83 9.7
ethoxide (75% + succinate)
______________________________________
The above process was repeated with the product from Example 1 using the
enhancement method (b) which achieved an allyloxy succinate yield of 97%.
The corresponding drying times were as follows:.
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Fresh Aged
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5.6 hours 5.4 hours
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